Block Sequence Effects on the Self-Assembly Behaviors of Polypeptide-Based Penta-Block Copolymer Hydrogels.

Peptide-based hydrogels have great potential for applications in tissue engineering, drug delivery, and so on. We systematically synthesize, characterize, and investigate the self-assembly behaviors of a series of polypeptide-based penta-block copolymers by varying block sequences and lengths. The copolymers contain hydrophobic blocks of poly(γ-benzyl-l-glutamate) (PBG, Bx) and two kinds of hydrophilic blocks, poly(l-lysine) (PLL, Ky) and poly(ethylene glycol) (PEG, EG34), where x and y are the number of repeating units of each block, where PBG and PLL blocks have unique functions for nerve regeneration and cell adhesion. It shows that a sufficient length of the middle hydrophilic segment capped with hydrophobic end PBG blocks is required. They first self-assemble into flower-like micelles and sequentially form transparent hydrogels (as low as 2.3 wt %) with increased polymer concentration. The hydrogels contain a microscale porous structure, a desired property for tissue engineering to facilitate the access of nutrient flow for cell growth and drug delivery systems with high efficiency of drug storage. We hypothesize that the structure of Bx-Ky-EG34-Ky-Bx agglomerates is beyond micron size (transparent), while that of Ky-Bx-EG34-Bx-Ky is on the submicron scale (opaque). We establish a working strategy to synthesize a polypeptide-based block copolymer with a wide window of sol-gel transition. The study offers insight into rational polypeptide hydrogel design with specific morphology, exploring the novel materials as potential candidates for neural tissue engineering.

Rapid template-free synthesis of nanostructured conducting polymer films by tuning their morphology using hyperbranched polymer additives.

Nanostructures in conducting polymer films can enhance charge carrier and ion transfer, provide porosity with high specific area and confer unique optoelectronic properties for potential applications. A general and facile synthesis has been developed to prepare nanostructured conducting polymer films without the need for using templates. This simple approach employs hyperbranched polymers as additives to tune the morphology of conducting polymer films into a continuous nanofibril network. Nanostructured conducting polymer films with improved crystallinity exhibit good charge carrier transport and stable nanofibril network, without sacrificing either property upon removing residual additives. Polymer field-effect transistor sensors have been used to demonstrate the benefits of the large surface area provided by the nanofibril network. The sensors with porous nanostructures exhibit lower detection limits (two times lower) and faster response times (33% faster) compared to the sensors without nanostructures. This general approach can advance the knowledge and development of nanostructured conducting polymer films for energy harvesting and storage, electronics, catalysts, sensors and biomedical applications.